Dimethylformamide → 3-Bromo-5-(tert-butyl-dimethyl-silanyloxy)-benzaldehyde

HRID 1513100Notes

Reaction equation

[C:1]([Si:5]([O:8][C:9]1[CH:14]=[C:13](Br)[CH:12]=[C:11]([Br:16])[CH:10]=1)([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].[Li]CCCC.CN([CH:25]=[O:26])C.[Cl-].[NH4+]>C1COCC1.C(OCC)(=O)C.CO>[Br:16][C:11]1[CH:12]=[C:13]([CH:14]=[C:9]([O:8][Si:5]([C:1]([CH3:2])([CH3:3])[CH3:4])([CH3:6])[CH3:7])[CH:10]=1)[CH:25]=[O:26]

Participants

Conditions

Temperature: -78 °C

Procedure

tert-Butyl-(3,5-dibromo-phenoxy)-dimethyl-silane (22 g; 60.08 mmol) was dissolved in THF (200 mL) in a dried reaction flask under an atmosphere of nitrogen. The mixture was cooled to −78° C. and n-BuLi (1.6 N in hexane; 41.25 mL; 66.09 mmol) was added while the temperature was kept between −60 and −78° C. The mixture was stirred for 15 min. and DMF (4.83 g; 66.08 mmol) was added. The reaction mixture was stirred for 1 h and methanol (5 mL) followed by saturated ammonium chloride was added. Etyl acetate (200 mL) was added and the organic phase was separated from the aqueous phase. The organic phase was washed with water, dried, and evaporated to dryness. The crude product was purified by flash chromatography (heptane: dichloromethane (1:1). Yield 7 g. HPLC-MS: m/z: 317.0 (M+1); Rt: 2.7 min.

Workup

customwas kept between −60 and −78° C
stirringThe reaction mixture was stirred for 1 h
additionwas added
customthe organic phase was separated from the aqueous phase
washThe organic phase was washed with water
customdried
customevaporated to dryness
customThe crude product was purified by flash chromatography (heptane: dichloromethane (1:1)

Sources & evidence

ORD record: ord-e5592e40bfff45fabe0aaa244e886102
Source dataset: uspto-grants-2012_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08217086B2

Reaction notes

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